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CN103502302A - Materials for optoelectronic devices - Google Patents

Materials for optoelectronic devices Download PDF

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Publication number
CN103502302A
CN103502302A CN201280020375.3A CN201280020375A CN103502302A CN 103502302 A CN103502302 A CN 103502302A CN 201280020375 A CN201280020375 A CN 201280020375A CN 103502302 A CN103502302 A CN 103502302A
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formula
polymkeric substance
structural unit
optoelectronic device
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CN103502302B (en
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J.J.相
P.M.小斯米格尔斯基
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BOE Technology Group Co Ltd
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General Electric Co
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Abstract

The invention discloses materials for optoelectronic devices. Energy efficient optoelectronic devices include an electroluminescent layer containing a polymer made up of structural units of formula I and II; wherein R1 and R2 are independently C22-44 hydrocarbyl, C22-44 hydrocarbyl containing one or more S, N, O, P, or Si atoms, oxaalkylaryl, or a combination thereof; R3 and R4 are independently H, C1-44 hydrocarbyl or Ci-44 hydrocarbyl containing one or more S, N, O, P, or Si atoms, or R3 and R4, taken together, form a C2-10 monocyclic or bicyclic ring containing up to three S, N, O, P, or Si heteroatoms; and X is S, Se, or a combination thereof.

Description

Material for optoelectronic device
statement about the research by federal government's patronage
The present invention is supported by government, the award of contract numbering DE-FC26-07NT43226 of american energy department.Government enjoys some right of the present invention.
Technical field
The present invention relates to the optoelectronic device field, particularly a kind of material for optoelectronic device (Optoelectronic Device).
Background technology
Two kinds of the most frequently used lightings are that incandescence shines and fluorescence illumination has consumed the energy of the U.S. over 5 quarts (Quads).Although these technology are ripe now and expection only realizes the increment improvement in performance, but to the expectation of inner illumination product (its characteristic has set the human consumer, light source should be cheap, there is the pleasant color and be easy to light modulation (white heat), or there is high efficiency and there is longer life (fluorescence)).Therefore, new illumination system not only must meet the existing expectation of human consumer to life-span, cost, easy-to-use degree, brightness and quality of colour, and should also provide will be good than prior art remarkable performance strengthen.Specifically, fluorescent-mercury lamp tool (Mercury fluorescent lamp) technology has quite high efficiency, and wherein almost 30% electric energy is converted into visible ray.Impressively in the modern technology based on mercury be, its efficiency is because need to produce high energy UV photon and can basically be restricted because of its shape on less degree, and this just requires to use to diminish illuminator structure (Lossy luminaire structures) and the light of reallocating usually.Therefore, to thering is quite high efficiency and can using the technology of minimum other means of illumination to offer an opportunity.Organic light emitting apparatus (OLED) be can the illumination of potential alternative mercury fluorescence technology.OLED is comprised of the one group of thin organic layer be positioned between two electrodes, and at least one in described two electrodes is transparent or semitransparent.By with the similar mode of LED, electric charge carrier is expelled to this organic layer from electrode, wherein these electric charge carriers compound (Recombine or Recombination) and emission are by the overflow light of described equipment of transparency electrode.Due to the active coating of equipment (about 100nm) as thin as a wafer, so OLED equipment is not independently usually, but manufactures at least 0.15mm is thick usually glass or polymeric substrate.Due to OLED equipment as thin as a wafer, therefore described OLED equipment can direct forming become desired shape, thereby avoids the means of illumination loss.Even more importantly, white luminous OLED does not produce the UV photon and can operate being low to moderate under the voltage of 3V.Therefore, the potential Energy Efficiency Ratio fluorescent-mercury lamp of oled light lighting system (light fixture+means of illumination) prodigiosin is imitated large twice.At present, the OLED that has a reported top efficiency is that power conversion efficiency is about 17% green equipment.The key factor of restriction OLED efficiency is external quantum efficiency (EQE), and described external quantum efficiency is launched photon and the electric charge carrier ratio of injecting.Because energy efficiency of equipment is the every other power loss entry product (product) in EQE and equipment, so the EQE value is determined the energy efficiency of equipment upper limit.Given typical white light OLED operating voltage and color property, require 30% power conversion efficiency and the 100LPW performance of about 50%EQE with coupling mercury fluorescence technique.Totally think, realize high EQE, OLED must meet two primary conditions.At first, all electric charges must be compound in equipment, thereby form the emission state that will produce light.The efficiency of this process is internal quantum (IQE).Secondly, the light that must will produce by luminance extracts air from the OLED active coating.All dropped into considerable development effort for light generation and light extraction.Exist the IQE value to be similar to the OLED equipment of one (unity), and report the scheme of many light extractions.Yet at present, the most effective OLED only has approximately 30% EQE, and these equipment not yet are converted into the stable white light light source.
Summary of the invention
Have been found that now the singlet emission that can carry out through aiming at and do not produce the conjugation fluorescent polymer of the loss caused because tri-state is compound.Therefore, on the one hand, the present invention relates to the polymkeric substance that the structural unit by formula I and II forms, and relates to the optoelectronic device with the electroluminescence layer that contains this base polymer,
R wherein 1and R 2be C independently 22-44alkyl, the C that contains one or more S, N, O, P or Si atom 22-44alkyl, oxa alkyl heteroaryl or its combination; R 3and R 4be H independently, C 1-44alkyl or the C that contains one or more S, N, O, P or Si atom 1-44alkyl, or R 3and R 4combine to form and contain the nearly C of three S, N, O, P or Si hetero atoms 2-10monocycle or dicyclo; And X is S, Se or its combination.
Wherein, X is S.
Wherein, X is Se.
Wherein, R 1and R 2c 22-44alkyl.
Wherein, R 1and R 2be-Ar (OCH 2cH 2(CH 2) m) noR 5, wherein, m is 0 or 1; The scope of n is approximately 20 and approximately between 500; And R 5it is low alkyl group.
Wherein, described formula I structural unit is
Figure BDA0000402055780000032
Wherein, described formula I structural unit is
Figure BDA0000402055780000033
r wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5; M is 0 or 1; The scope of n is approximately 20 and approximately between 500; And R 5it is low alkyl group.
Wherein, described formula I structural unit is
Figure BDA0000402055780000034
wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5; The scope of n is approximately 20 and approximately between 500; And R 5it is low alkyl group.
Wherein, described formula I structural unit is
Figure BDA0000402055780000041
wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5; The scope of n is approximately 20 and approximately between 100; And R 5it is low alkyl group.
Wherein, described formula II structural unit is
Wherein, described formula II structural unit is
Figure BDA0000402055780000043
Wherein, described formula II structural unit is
The present invention also provides a kind of polymkeric substance that comprises formula I and II structural unit,
Figure BDA0000402055780000045
Wherein, R 1and R 2be C independently 22-44alkyl, the C that contains one or more S, N, O, P or Si atom 22-44alkyl, oxa alkyl heteroaryl, or its combination; R 3and R 4be H independently, C 1-44alkyl or the C that contains one or more S, N, O, P or Si atom 1-44alkyl, or R 3and R 4combine to form and contain the nearly C of three S, N, O, P or Si hetero atoms 2-10monocycle or dicyclo; And X is S, Se or its combination.
Wherein, X is S.
Wherein, X is Se.
Wherein, R 1and R 2c 22-44.
Wherein, R1 and R2 are-Ar (OCH 2cH 2(CH 2) m) noR 5, wherein, m is 0 or 1; The scope of n is approximately 20 and approximately between 500.
Wherein, described formula I structural unit is
Wherein, described formula I structural unit is
Figure BDA0000402055780000052
r wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5; M is 0 or 1; The scope of n is approximately 20 and approximately between 500; And R 5it is low alkyl group.
Wherein, described formula I structural unit is
Figure BDA0000402055780000053
wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5; The scope of n is approximately 20 and approximately between 500; And R 5it is low alkyl group.
Wherein, described formula I structural unit is
Figure BDA0000402055780000054
wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5; The scope of n is approximately 20 and approximately between 100; And R 5it is low alkyl group.
Wherein, described formula II structural unit is
Wherein, described formula II structural unit is
Figure BDA0000402055780000062
Wherein, described formula II structural unit is
Figure BDA0000402055780000063
The present invention provides again a kind of compound with following formula,
Figure BDA0000402055780000064
R wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5; M is 0 or 1; The scope of n is approximately 20 and approximately between 500; And X when occurring, be independently at every turn halogen, trifluoromethayl sulfonic acid ,-B (OH) 2,-B (OR) 2,-BO 2r or its combination; And R is alkyl or alkylidene group.
Wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5; The scope of n is approximately 20 and approximately between 500; And R 5it is low alkyl group.
Wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5; The scope of n is approximately 20 and approximately between 100; And R 5it is low alkyl group.
Wherein, comprise in addition containing the iridium organometallic compound.
Wherein, described containing iridium organometallic compound and described mixed with polymers.
It is a kind of for pure 9 that the present invention provides again, the method for 9-substituted fluorene compound, and described method is included in to exist in the strong acid situation described fluorene compound is contacted with strong oxidizer.
Wherein, described strong oxidizer is chromic oxide.
The accompanying drawing explanation
Fig. 1 is the schematic section according to optoelectronic device of the present invention.
Fig. 2 A is according to the light absorption of polymkeric substance and the figure of emmission spectrum of illustrating of the present invention.
Fig. 2 B and 2C are the figure that photoluminescence spectra is shown according to of the present invention, wherein film and the solution of polymkeric substance are compared.
Fig. 3 is the figure that describes the decay of luminescence of polymkeric substance after photoexcitation according to of the present invention.
Fig. 4 A to 4C is the solution decay of luminescence curve of polymkeric substance according to the present invention in chlorobenzene solution.
Fig. 5 A to 5C is according to film of the present invention or polymer light-emitting extinction curve.
Fig. 6 is the figure of comparison according to the time-resolved emission spectrum of polymkeric substance of the present invention and prior art polymkeric substance.
Fig. 7 is the figure that the electroluminescent spectrum measured for optoelectronic device is shown according to of the present invention.
Embodiment
Extraction efficiency loss major cause in phosphorescence equipment is that Energy Coupling is in the plasma model of metallic cathode.OLED based on conjugated polymers has fluorescence (singlet) the emission kind of aiming at electrode plane usually, and therefore may have high extraction efficiency and because being coupled on the plasma model loss of the lower calculating caused.Yet these these equipment have low IQE because with tri-state again the electric charge carrier of combination do not launch, this has just offseted it and has aimed at advantage.
A kind of verified aligning advantage of extracting method use fluorescence (singlet emission) polymeric film of light from active mechanical floor.In order to improve fluorescence equipment, must improve IQE by forcing all electric charge carriers compound under singlet (Recombine or Recombination).The method of the IQE of the singlet emission in a kind of OLED of increasing is called " superfluorescence (Extra-fluorescence) ".Superfluorescence is by inserting and working just like the mixolimnion of the heavy metal of iridium.Layer in addition is location in the following manner: make it only affect charge transfer (Charge Transfer; Be called for short CT) state, described charge transfer state is the precursor of exciton.By allowing these exciton precursors to mix, meeting under some energy rank restraint condition, can suppress non-emissive tri-state and form.The OLED of the fluorescent material based on through aiming at can have the high IQE value identical with OLED based on phosphor material because of superfluorescence.
A kind of organic photoelectric equipment contains a plurality of layers usually, and wherein, in the simplest situation shown in Fig. 1, it comprises anode layer 4 and respective cathode layer 2, and wherein organic electro luminescent layer 3 is arranged between described anode layer and described cathode layer.Described equipment is to be enclosed in to be encapsulated between layer 1 and transparent substrate 5.This kind equipment illustrates by organic light emitting apparatus and organic photovoltaic (OPV) equipment.When on the OLED electrode, applying voltage bias, by negative electrode, electron beam is mapped in electroluminescence layer, remove the electronics (or hole (Holes) is expelled to electroluminescence layer) from electroluminescence layer from anode simultaneously.When hole and electronics in electroluminescence layer in conjunction with the time, occur luminous.Similarly, when OPV equipment absorbs photon energy, the combination and produce electromotive force between anode and negative electrode in photoresistance of hole and electronics.
When electronics is combined, form singlet or tri-state exciton when hole in the electroluminescence layer of OLED equipment, and the singlet exciton is transferred to energy among environment by attenuation.Different from the singlet exciton, the tri-state exciton can not experience attenuation usually, and therefore all not luminous except under extremely low temperature.Therefore, forming the tri-state exciton means usually in envrionment temperature or approach the basic restriction of the organic light emitting apparatus efficiency operated under envrionment temperature.Can avoid forming unproductive tri-state exciton by preventing the direct charge recombination on polymkeric substance according to polymkeric substance of the present invention.In this case, from the emission of polymkeric substance will only come from the to hang oneself non-radiative energy transfer process of the tri-state that excites.For example, the molecular energy with blue emission tri-state is transferred to energy according to polymkeric substance of the present invention in non-radiative mode, and this polymkeric substance then produces than low-energy radiation.
In special specific embodiments, this polymkeric substance comprises the structural unit derived from the fluorenes monomer, and this fluorenes monomer has the organic substituent that is greater than fluorenyl, especially chain alkyl or oxa alkyl in 9,9-position.Believed the emitting area that this substituting group can isolation polymer and impel their to aim at.Exactly, in thering is the structural unit of chain alkyl, the R in formula II 1and R 2c 22-44alkyl.More exactly, in some embodiments, formula I structural unit is
In the structural unit with long-chain oxa alkyl, the R in formula II 1and R 2be all-Ar (OCH 2cH 2(CH 2) m) noR 5, wherein m is 0 or 1; The scope of n is approximately between 20 and 500, and R 5low alkyl group (Lower alkyl).More exactly, the structural unit of formula I can be
Figure BDA0000402055780000092
R wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5, m is 0 or 1; The scope of n is approximately 20 and approximately between 500, and R 5it is low alkyl group.More exactly, the structural unit of formula I can be
PEG Shi – CH wherein 2cH 2(OCH 2cH 2) n; And the scope of n is approximately 20 and approximately between 500.The molecular weight of PEG group is also indecisive and can be in embodiments approximately 2000 dalton or approximately 10500 dalton (Daltons).The invention still further relates to the monomer for the preparation of polymkeric substance, this polymkeric substance has the unit derived from fluorene compound, and Suo Shu Ti compound comprises oxa alkyl in 9,9-position.These monomers have following formula:
R wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5; M is 0 or 1; The scope of n is approximately 20 and approximately between 500; X when occurring, be independently all at every turn halogen (halo), triflate (Triflate) ,-B (OH) 2,-B (OR) 2,-BO 2r or its combination; And R is alkyl or alkylidene group (Alkylene).
The structural unit example of formula II comprises
Figure BDA0000402055780000101
According to the molecular weight Mn of polymkeric substance of the present invention about 1000 dalton and approximately between 200000 dalton, and molecular weight Mw about 10000 dalton to approximately between 100000 dalton.More specifically, the scope of molecular weight Mw about 2000 dalton to approximately between 100000 dalton.
Described polymkeric substance also can comprise the structural unit of the formula except formula I or II.Especially suitable comonomer comprises the UUS6 that transfers Dao Er company (Dow), the triarylamine (Triarylamines) of describing in 309,763 and US6,605,373.
Electroluminescence layer also can comprise triarylamine, polyvinyl carbazole (Polyvinylcarbazoles) or contain the homopolymer of the luminous organometallic complex of iridium.These other materials can or may reside in polymkeric substance with polymer blending of the present invention and carry out in connected layer that entity contacts.Suitable iridium complex for example comprises the iridic compound be comprised of organic Cyclometalated part (Organic cyclometallated ligand) and ketone pyrrole ligand (Ketopyrrole ligand) purchased from General Electric Corporation (General Electric), as the iridium complex of describing in WO2008/014037.Other available exemplary complex compounds are at US6, are described in 048,630, US6,097,147, US6,303,238, US6,830,828 and US6,894,307.
Except anode, negative electrode and luminescent material, the miscellaneous part that can be present in organic light emitting apparatus comprises hole injection layer, electronics injecting layer and electron transfer layer.At the organic light emitting apparatus run duration that comprises electron transfer layer, the most of electric charge carriers (that is, hole and electronics) that are present in electron transfer layer are electronics, and can be luminous via the hole and the compound of electronics that are present in electron transfer layer.The other parts that can be present in organic light emitting apparatus comprise hole transmission layer, hole transport emission (Emission or Emitting) layer, hole blocking layer and electric transmission emission layer.
Organic electro luminescent layer is the layer of organic light emitting apparatus inside, when in operation, and the electronics that it contains larger concentration and hole, and provide exciton to form and luminous position.The hole injection layer is the layer usually contacted with anode, and it promotes hole to be expelled to the layer of OLED inside from anode; And the electronics injecting layer is the layer usually contacted with negative electrode, and it promotes that electronics is expelled to OLED from negative electrode.Hole injection layer or electron transfer layer are all without contacting with negative electrode.Usually, electron transfer layer is not effective hole transport thing, and therefore in order to blocking hole towards cathodic migration.Electron transfer layer is to promote electronics to be transmitted to the layer at charge recombination position from negative electrode.Hole transmission layer is when OLED is in operation, to promote hole to conduct to the charge recombination position and needn't contact the layer of anode from anode.The hole transport emission layer is such layer: when OLED is in operation, promote hole-conductive to compound position, and most of electric charge carriers are holes, and emission also can be shifted and occur via the energy of the charge recombination zone at the elsewhere place in slave unit not only via the compound generation with residual electrons.The electric transmission emission layer is such layer: when OLED is in operation, promote electronic conduction to the charge recombination position, and most of electric charge carriers are electronics, and emission also can be shifted and occur via the energy of the charge recombination zone at the elsewhere place in slave unit not only via the compound generation with residual indentation.
Being suitable for material as anode comprises as having per square inch of being measured by the four-point probe technology material at least about the cubic conductance of 100 ohm.Tin indium oxide (ITO) is usually as anode, because it is substantially transparent and therefore promote from the effusion of the light of electroactive organic layer emission for optical transmission.Other material that can be used as anode layer comprises stannic oxide, Indium sesquioxide, zinc oxide, indium zinc oxide, zinc indium tin oxide, weisspiessglanz and composition thereof.
Be suitable for comprising zero-valent metal as the material of negative electrode, it can be expelled to negative charge carriers (electronics) in the OLED internal layer.Be suitable for comprising K, Li, Na, Cs, Mg, Ca, Sr, Ba, Al, Ag, Au, In, Sn, Zn, Zr, Sc, Y, lanthanon, the alloy of above-mentioned and the mixture of above-mentioned as the various zero-valent metals of negative electrode.Applicable alloy material as cathode layer comprises Ag-Mg, Al-Li, In-Mg, Al-Ca and Al-Au alloy.The non-alloy structure of stratification also can be used for negative electrode, the thin layer of the thin metal layer of like calcium or the metal fluoride of like LiF, and described thin layer is covered by the more thin layer of the zero-valent metal as aluminium or silver.Specifically, negative electrode can be comprised of single zero-valent metal and especially aluminum metal.
Be suitable for use in material in the hole injection layer and comprise that (purchased from HC Stark company (H.C.Stark, Inc.), trade name is for 3,4-Ethylenedioxy Thiophene (PEDOT) and PEDOT and sodium polystyrene sulfonate (PSS) ) blend, and comprise the polymkeric substance (purchased from air chemical company (Air Products Corporation)) based on thieno-[3,4b] thiophene (TT) monomer.
The material be suitable for use in hole transmission layer comprises two ((two-4-Yue tolyl amido) phenyl) hexanaphthenes of 1,1--, N, two (4-the aminomethyl phenyl)-N of N'-, two (4-ethylphenyl)-(1,1'-(3,3'-, the bis-Yue methyl) biphenyl)-4 of N'-, the 4'-diamines, four-(3 aminomethyl phenyl)-N, N, N', N'-2,5-phenylenediamine, phenyl-4-N, N-phenylbenzene amido vinylbenzene, to (diethylin) phenyl aldehyde diphenyl hydrazone, triphenylamine, 1-phenyl-3-(p-(diethylin) styryl)-5-(p-(diethylin) phenyl) pyrazoline, trans-two (9H-carbazole-9-yl) tetramethylene of 1,2-, N, N, N', N'-tetra-(4-aminomethyl phenyl-(1,1'-biphenyl)-4,4'-diamines, copper phthalocyanine, Polyvinyl carbazole, (phenyl methyl) polysilane, gather (3,4-Ethylenedioxy Thiophene) (PEDOT), polyaniline, Polyvinyl carbazole, the triaryl diamines, the tetraphenyl diamines, aromatic uncle amine, hydrazone derivative, carbazole derivative, triazole derivative, imdazole derivatives, oxadiazoles derivative and Polythiophene with amido, as United States Patent (USP) the 6th, disclosed in 023, No. 371.
The material that is suitable as electron transfer layer comprises poly-(9, the 9-dioctyl fluorene), three (8-hydroxyquinone perester radical) aluminium (Alq3), 2,9-dimethyl-4,7-phenylbenzene-1,1 coffee quinoline, 4,7-phenylbenzene-1,10-coffee quinoline, 2-(4-xenyl)-5-(4 tert-butyl-phenyl)-1,3,4-oxadiazoles, 3-(4-xenyl)-4-phenyl-5-(4-tert-butyl-phenyl)-1,2,4 triazoles, containing the polymkeric substance of 1,3,4-oxadiazoles, containing 1, the polymkeric substance of 3,4-triazole, containing quinoline polymkeric substance and the cyano group PPV of quinoline.
In the US20040118444 that OPV equipment is " large-area photovoltaic apparatus and manufacture method thereof (Large-Area Photovoltaic Devices and Methods of Making Same) " at the title that for example transfers General Electric Corporation, be described, above-mentioned document is incorporated to this paper in full with it by reference.OPV equipment can comprise two translucent charge-conduction electrodes, and one of them serves as the positive charge collector, and another serves as the negative charge collector, and has organic membrane between two electrodes.Electrode can be by as SnO 2, ZnO 2, tin indium oxide doping metal oxide thin film form, or it can be by using as the thin metal film of the element of silver, gold or aluminium form.Can prepare with physical vapor deposition or via the dash coat technology by conductive electrode.Produce one or more organic materialss of charged carrier after between electrode, absorb light can being had.Usually, charge separation realizes in the following manner: by the bi-material juxtaposition so that the steady state (charge carriers, electron acceptor(EA)) of electronics be therein on a kind of material and hole (positive charge carriers, electron donor) be on another kind of material.A right example of materials is 3,4,9,10-, bis-naphthalene tetracarboxylic acid bisbenzimidazoles (PTCBI, electron acceptor(EA)) and copper phthalocyanine (CuPc, electron donor).Another may material (2-methoxyl group-5-(3,7' dimethyl octyloxy) Isosorbide-5-Nitrae phenylene-vinylidene (MDMO-PPV) and (6,6) phenyl-C61-methyl-butyrate (PCBM) poly-to comprising.In addition, also can use the hybrid structure formed by organic components (as, polyphenylene-vinylidene derivative) with as the inorganic nanocrystal of the material of CdSe or ZnTe.This type of Nanocrystalline materials size and shape is transformable, and it can be varied to size from about 2nm spheroid is the high aspect ratio bar of micron dimension, or even can have a plurality of high aspect ratio bars that are connected to single core.Electron donor and acceptor material can be deposited in discrete stratification structure or be blended together.
OPV equipment can be comprised of many layers, and wherein each layer thickness can be changed to several microns from several nanometers.The typical thickness of organic layer is about 10nm to 100nm.Can or prepare via physical gas phase deposition technology by solution-treated by this type of multi-layer device.Multilayer can form in the following manner through the device of solution-treated: with the insoluble solvent of separating lower floor, carry out coating material continuously.Suitable the first layer through the equipment of solution-treated is to be not dissolved in poly-(3 in many organic solvents, the inferior ethylene dioxythiophene of 4-): poly-(styrene sulfonic acid) makes subsequently by the blend of (MDMO-PPV and the PCBM) of the deposition of the organic solvent as chlorobenzene.The multilayer organic structure also can form by continuous thin organic membrane physical vapor deposition, and this continuous thin organic membrane can be by one or more component molecular compositions.In the photorectifier situation based on non-crystalline silicon, can adjust the general thickness of organic layer, in order to obtain the required mark of charge integration signal with respect to the photon counting signal.
For clearer and describe concisely and point out to provide the subject matter of advocated invention to give a definition for particular term.
" aryl (Aryl) " and " heteroaryl (Heteroaryl) " means to contain 5 or 6 yuan of aromatic rings or the heteroaromatic rings of 0 to 3 hetero atom being selected from nitrogen, oxygen or sulphur; 9 or the 10 yuan of aromatic rings of two rings or the heteroaromatic rings system that contain 0 to 3 hetero atom that is selected from nitrogen, oxygen or sulphur; 13 or the 14 yuan of aromatic rings of three rings or the heteroaromatic rings system that perhaps contain 0 to 3 hetero atom that is selected from nitrogen, oxygen or sulphur.6 to 14 yuan of carbocyclic rings of aromatics for example comprise benzene, naphthalene, indane, tetraline and fluorenes; And 5 to 10 yuan of heteroaromatic rings comprise, for example, imidazoles, pyridine, indoles, thiophene, chromene, thiazole, furans, benzoglyoxaline, quinoline, isoquinoline 99.9, quinoxaline, pyrimidine, pyrazine, tetrazolium and pyrazoles.Stretching aryl refers to divalence and removes by two carbon potentials from aromatic ring the group that hydrogen forms.Arylidene refers to the alkylidene unit replaced with aryl.
" arylalkyl (Arylalkyl) " refers to the aromatic yl residue be attached on aryl rings.Example is phenmethyl and styroyl.Heteroarylalkyl refers to the alkyl residue be attached on heteroaryl ring.Example comprises pyridylmethyl and pyrimidinylethyl.Alkylaryl refers to aromatic yl residue, and described aromatic yl residue has the one or more alkyl attached with it.Example is tolyl and Lai Ji.
" alkoxyl group " (Alkoxy or Alkoxyl) refers to the group that is attached to 1 to 8 carbon atom with straight chain, side chain or cyclic configuration and combination thereof of precursor structure by oxygen.Example comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, ring propoxy-and cyclohexyloxy.Lower alkoxy refers to the group that comprises one to four carbon.
" acyl group (Acyl) " refers to the group that is attached to 1 to 8 carbon atom with straight chain, side chain, ring-type configuration, saturated, unsaturated and aromatics and combination thereof on precursor structure by the carbonyl functional group.One or more carbon in acyl residue can be substituted by nitrogen, oxygen or sulphur, and needing only with the attachment point of parent is to remain on carbonyl.Example comprises ethanoyl, benzoyl, propionyl, isobutyryl, tert-butoxycarbonyl and carbobenzoxy-(Cbz).Lower acyl refers to the group that comprises one to four carbon.
" heterocycle (Heterocyclic) " refers to cycloalkyl or aromatic yl residue, and wherein the one or both in carbon atom is substituted by the hetero atom as oxygen, nitrogen or sulphur.Heterocycle example in scope of the present invention comprises: tetramethyleneimine, pyrazoles, pyrroles, indoles, quinoline, isoquinoline 99.9, tetrahydroisoquinoline, cumarone, benzo dioxane, benzo dioxole (while occurring as substituting group, being commonly referred to methylenedioxyphenyl), tetrazolium, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furans, oxazole, azoles quinoline, isoxzzole, dioxane and tetrahydrofuran (THF).
" (Substituted) that be substituted " refers to residue, include, but is not limited to the residue of alkyl, alkaryl, aryl, arylalkyl and heteroaryl, wherein the H atom of residue up to three is by low-carbon alkyl, the alkyl be substituted, aryl, the aryl be substituted, haloalkyl, alkoxyl group, carbonyl, carboxyl, carboxylic alkoxyl group, carboxamide groups, acyloxy, amidino groups, nitro, halogen, hydroxyl, OCH (COOH) 2, cyanogen, primary amino, secondary amino group, amide group, alkylthio, sulfoxide, sulfone, phenyl, phenmethyl, phenoxy group, benzyloxy, heteroaryl or heteroaryloxy.
" haloalkyl " refers to alkyl residue, and wherein halogen atom substitutes one or more hydrogen atom; The term haloalkyl comprises whole haloalkyl.Haloalkyl example in scope of the present invention comprises CH 2f, CHF 2and CF 3.
" oxa alkyl (Haloalkyl) " refers to alkyl residue, and wherein one or more carbon is to be substituted by oxygen.It is to be attached on precursor structure via alkyl residue.Example comprises methoxy propoxy, 3,6,9-tri-oxygen decyls with and analogue.The term oxa alkyl refers to such compound: wherein oxygen is to bond on its contiguous atom (formation ehter bond) via singly-bound; It not refers to doubly linked oxygen, as visible in carbonyl.Similarly, thia alkyl and azepine alkyl refer to that wherein one or more carbon substitute by sulphur or nitrogen respectively alkyl residue.Example comprises ethylamino-ethyl and methyl sulfo-propyl group
Example
All processing of material and characteristic air-sensitive material are to carry out under dry nitrogen atmosphere.All solvents are purchased from taking house scientific company (Fisher Scientific), and unless otherwise noted, otherwise use not being further purified in situation.Unless otherwise noted, otherwise all reagent purchased from Sigma-aldrich company (Sigma-Aldrich) and not being further purified in situation, use. 1h NMR spectrum is to obtain on the Avance400MHz NMR of Brooker company (Bruker).The mixed bed C post of GPC by polymkeric substance laboratory company (Polymer Laboratories) by chloroform as mutually mobile and reference standard polystyrene and in the upper acquisition of the 1100GPC of Agilent company (Agilent).HPLC moves to come mutually with water/acetonitrile with Zorbax Eclipse XDB-C8 post and obtains on the 1100HPLC of Agilent company.Absorption spectrum carrys out record with Varian Cary300 scanning UV-visible spectrophotometer.
Table 1
Figure BDA0000402055780000161
Material
4,7-bis-is bromo-2,1, and 3-diazosulfide (BTD) (1): the described programs of people such as poplar (Yang) are for the preparation of (l) (poplar R.(Yang, R.); Field R.(Tian, R.); Tight J.(Yan, J.); Open Y.(Zhang, Y.); Poplar J.(Yang, J.); Wait Q.(Hou, Q.); Poplar W.(Yang, W.); C.(Zhang, C.) and Cao Y.(Cao, Y.), " polymer " (Macromolecules), 2005,8,244).
4,9-dibromo naphthols [2,3-c] [1,2,5] thiadiazoles (NTD) (2)): the described programs of people such as (Wei) of defending is for the preparation of (2) (defending P.(Wei, P.); Section L.(Duan, L.); Open D.(Zhang, D.); Tall J.(Qiao, J.); King L.(Wang, L.); King R.(Wang, R.); Dong G.(Dong, G.) and Kui .Y.J.(Qui, Y.J.), " materials chemistry " (Mater.Chem.), 2008,18,806).
4,7-bis-is bromo-2,1, and 3-benzo arsenic diazole (BSeD) (3): the described programs of people such as poplar (Yang) are for the preparation of (3) (poplar J.(Yang, J.); River C.(Jiang, C.); Open Y.(Zhang, Y.); Poplar R.(Yang, R.); Poplar W.(Yang, W.); Wait Q.(Hou, Q.) and Cao Y.(Cao, Y.), " polymer ",, 37,1211 in 2004).
4,9-dibromo naphthols [2,3-c] [1,2,5] arsenic diazole (NSeD) (4): the described programs of people such as Lay grace Hart (Reinhart) are for the preparation of (4) (Lay grace Hart B.(Reinhardt, B.); Cloth rood L.(Brott, L.); Ka Er fast S.(Clarson, S.); Deere is strangled special A.(Dillard, A.); Hart J.(Bhatt, J.); Block southern R.(Kannan, R.); Former L.(Yuan, L.); What G.(He, G.) and Eswar Prasad P.(Prasad, P.), " materials chemistry ", 1998,10,1863).
2,3-, bis-amido naphthalenes are purchased from 3B scientific company (3B Scientific Corporation), and use not being further purified in situation.
Example 1:2,7-bis-is bromo-9,9-docosyl-9H fluorenes (F22-dibromide) (5)
The tall described programs of people such as (Jo) is suitable for preparation (5) (tall J.(Jo, J.); Pond C.(Chi, C.); Lattice S.(Hoger, S. suddenly); Temperature lattice G.(Wegner, G.) and Yin D.(Yoon, D.) " Europe chemistry " (Chem.Eur.J.), 2004,10,2681).2, the bromo-9H fluorenes 9 (16.2g of 7-bis-, 50mmol), potassiumiodide (80mg, 5mmol), potassium hydroxide is (from the 86.2%KOH of JT Bark company (J.T.Baker), 16.3g, 250mmol) and the mixture of methyl-sulphoxide (100mL) in the three neck round-bottomed flasks of 250mL, by magnetic force, stirred.With this flask of nitrogen purge 15 minutes, and add 1-bromo docosane (50.6g, 130mmol).Flask is heated to 60 ℃ and stirred overnight.Hot solution is watered on ice, and with 1 liter of hexane, product is extracted.The hexane extraction material is by normal saline washing, through MgSO 4drying and process solution evaporation, thus 40 gram canescence (off-white) powder obtained, and this pale powder is comprised of described product and remaining 1-bromo docosane.Finally decolour by thering is the 50mL hexane/sulfuric acid (25/25) of 250mg chromic oxide, 5 gram products being heated and realized in 30 minutes.Hexane layer is collected, and then water rinses three times, and then by acidic alumina, filters.Rinse this aluminum oxide with the hexane of 40mL heat.Rotary evaporation to solvent produces 4 gram pure white products.If trace 1-bromo docosane is still by ethyl acetate or the extra recrystallize of butylacetate, provide so the pure products on spectroscopy.
Example 2:2, two (4,4,5,5-tetramethyl--1,3, the 2-dioxa boron penta ring-2-yls)-9 of 7-, 9-docosyl fluorenes (F22-biborate) (6)
Biborate (6) is used the modified version of tall people's program therebies such as (Jo) originally synthetic.In the 250mL round-bottomed flask, by dibromide (5) (6g, 6.4mmol) with two (tetramethyl ethylene ketone base) two boron (9.8g > 38.6mmol), Potassium ethanoate (3.79g, 98.15mmol), 2-dicyclohexyl phosphino--2 ', 6 '-dimethoxy-biphenyl (SPhos) (262mg, 0.638mmol) combines in the anhydrous THF of 100mL.With this solution of nitrogen purge 30 minutes, and add Pd (II) Cl 2(45mg, 0.26mmol), and make reaction reflux 4 hours.Once cooling, will remove THF by rotary evaporation, and by the hexane extraction residual substance.Extracting substance is through diatomite filtration, and concentrated subsequently.By heptane, silica gel is carried out to chromatography, thereby obtain 5.54 grams (84% productive rate) pure products.
The general polymerization program
The general of the polymkeric substance that scheme 1. contains BTD and BSeD synthesized
Figure BDA0000402055780000181
The general of the polymkeric substance that scheme 2. contains NTD and NSeD synthesized
Figure BDA0000402055780000191
Polymkeric substance is that the method for summarizing in operational version 1 or 2 is synthetic, also uses in due course following program synthetic:
Before weighing, all monomers in vacuum drying oven with 50 ℃ of dryings at least 2 hours.25ml double-neck flask and magnetic stirrer with the nitrogen inlet to bubbler are equipped with all monomers, SPhos and 5ml toluene.This solution is used degassed 5 to 10 minutes of nitrogen, then uses residual toluene to rinse Weighing funnel, thereby adds Pd (OAc) 2.Simultaneously, in independent bottle, aqueous components is degassed by nitrogen.After degassed at least 15 minutes, add aqueous components to organic solution, and flask is immersed in 70 ℃ of oil baths.Stir and heating and continuous 16 to 20 hours under positive nitrogen pressure, now, add 20mg4-ethyl-phenyl-boron dihydroxide.After one hour, add 100L normal-butyl-4-benzene iodide.After one hour, allow mixture cooling, and dilute this mixture with toluene and the water of each about 10ml subsequently again.Mixture is transferred to separating funnel, abandons water and rinse organic phase with 3x50ml water and the saturated NaCl of 1x50ml.Subsequently, transmit organic solution by the funnel that contains infusorial earth and drierite ze, and stir filtered solution at least 30 minutes, by containing the Mercaptofunctional filtered through silica gel, and now and stirred overnight together with the sodium borohydride of several milligrams.Solution filters and is concentrated on rotatory evaporator the volume of about 5ml again, is loaded into subsequently on the saturated silica gel filter cylinder of toluene.Polymkeric substance be the post from thering is toluene (about 100ml) wash-out out, and toluene solution is concentrated into about 5ml.By fierce stirring, make solution precipitation in the methyl alcohol of 10 volumes, polymkeric substance separates.Polymkeric substance is collected, is used methyl alcohol to be rinsed by filtration, and is that to carry out the universe in 40 to 50 ℃ of vacuum drying ovens dry.
Example 3 to 9: polymkeric substance is synthetic
For F22 90-BTD 10(P1) synthetic reagent is shown in table 2.Amount for the preparation of the monomer of the polymer P 2 to P6 in table 3 is adjusted according to required polymer composition.
Table 2
Figure BDA0000402055780000201
All polymkeric substance are characterized by GPC, and if find lower molecular weight shape of tail structure, so by the polymkeric substance fractionation precipitation in butylacetate.The polymkeric substance of the molecular weight of reporting and productive rate reflection classification.Polymer P 6 and P7 produce oligomerization (oligomer) product that is not suitable for this research.It should be noted that the standard method according to people, along with the monomer band gap reduces, the polymerizability of system reduces, and this can be by reducing productive rate and molecular weight indication.As expected, people see that the longer molecular weight caused because of aromatics diazole part (Aromatic diazole moiety) absorbs.In addition, can observe the blue shift in the absorption that is derived from the fluorene skeleton that wherein the aromatics diazole increases, this is because average fluorenes block length reduces.
Table 3:GPC, productive rate and UV/V are the signs of synthetic polymkeric substance.
The index number Polymkeric substance Title Mw、Mn、pd Productive rate % UV peak value (nm)
3 P1 F22 90-BTD 10 117k、60k、2.0 50% 385，447sh
4 P2 F22 70-BTD 30 111k、50k、2.2 74% 366，450
5 P3 F22 90-BSeD 10 83.8k、39.1k、2.1 68% 382，460
6 P4 F22 70-BSeD 30 54.8k、28.8k、2.2 62% 367，471
7 P5 F22 90-NTD 10 48.6k、24.5k、2.0 25% 385，509
8 P6 F22 70-NTD 30 Mn<5k <10% NA
9 P7 F22 90-NSeD 10 OP <10% NA
OP=oligomerization product, the sh=shoulder, NA=is disabled
Example 10: polyoxyethylene glycol 4, the preparation of 4'-(the bromo-9H-fluorenes-9 of 2,7-bis-, 9-bis-bases) diphenol
Figure BDA0000402055780000211
Polyoxyethylene glycol 4,4'-(the bromo-9H-fluorenes-9 of 2,7-bis-, 9-bis-bases) diphenol (dibromo BPF) is prepared as follows.Dibromo BPF (0.407g, 0.8mmol) and methylsulfonyl PEG-5000 monomethyl ether (10g, 2.0mmol) are refluxed in the acetone with salt of wormwood (0.276g, 2.0mmol) at 50mL.This reaction is heated 4 days when refluxing, and now, reaches the quantitative conversion of being determined by HPLC.Solvent removes by rotary evaporation, and residual substance is used dichloromethane extraction.The methylene dichloride water rinses twice and rinses once by saturated aqueous sodium chloride.The dichloromethane solution dried over mgso, and solvent removes by rotary evaporation, thus obtain the polyoxyethylene glycol product containing the remaining methylsulfonyl PEG-5000 of 30wt% that has an appointment.Monomer is used not being further purified in situation.In 1H NMR 3.61 and the peak value at 3.36ppm place can not correctly quadrature because the molecular weight of PEG5000 is inaccurate and remaining methylsulfonyl PEG still stays in product.1H NMR(400MHz, CD2Cl2) 7.66(d, 2H), 7.53-7.49(m, 4H) 7.47(d, 4H), 6.82(d, 4H), 3.61(s, about 1270H), 3.36(s, 8H).
Photophysics with the polymkeric substance of long alkyl group side chain
General procedure
Spectrum after the optical excitation of polymkeric substance and temporal resolution kinetics are used the instrument F920 of Edinburg company (Edinburgh) photofluorometer in 469nm(gram Qazz company (Picoquant), about 70ps pulsewidth) or 355nm (about 500ps pulsewidth JDS Uniphase Corp. (JDS Uniphase)) under with pulse laser, excite to obtain.Detector is through the MCP-PMT of spectrum correction R3809(shore pine company (Hamamatsu)).Chlorobenzene (aldrich company) is as the solvent medium of the solution of test material.Adjust strength of solution, so that the optical density(OD) of different solutions is less than 1.0 in the 450nm-470nm scope.
The general procedure for preparing clean film be using the material dissolves of 1% solution as polymkeric substance in the aromatic solvent as toluene, dimethylbenzene or chlorobenzene, and via rotational casting, be deposited on subsequently on clean quartz slide.The typical case is revolved speed between 0.8krpm and 3krpm.Allow film dry before use, but generally can not carry out heating power annealing.During photoluminescence experiment, film is placed in the nitrogen atmosphere through purifying to stop experimental session because of may degrading that photo-oxidation causes.
Example 11: solution luminescent spectrum
Example 4(P2), example 6(P4) and example 7(P5) the solution Absorption and emission spectra of polymkeric substance shown in Fig. 2 A.Maintain in whole experiment that instrument is aimed at and intensity, and therefore the photoluminescence integrated intensity has direct comparability and can be for relative photoluminescence quantum yield is provided.The BTD-30 sample has high-luminous-efficiency, and therefore luminous quantum efficiency relates to the BTD-30 sample.Spectrum shows to launch shifts to longer wavelength, and this is because selenium replaces sulphur and conjugation increases caused via the phenyl on naphthyl substituted dithiazole comonomer.
The luminescent spectrum of polymeric film is shown in Fig. 2 B and 2C.The emission wavelength of observing in 500nm to 700nm scope in these spectrum is consistent with the feature of observing in same wavelength ranges in the solution phase spectrum.Along with comonomer (that is, BTD, NTD, BSeD, NSeD) relative proportion increases, people also observe the little skew in the (not shown) luminescent emission maximum.
Example 12: the time resolved spectroscopy of pure material
The luminous behavior of polymkeric substance is also depended on comonomer and for the relative load of fluorenes monomer.Fig. 3 illustrates the optical excitation decay of luminescence curve of BTD multipolymer shown in example 3 and 4 afterwards.Also shown is after being excited the F22-BTD-30 polymkeric substance (example 4) in solution and by derived from 9 under 468nm, the corresponding decay of luminescence curve of the polymkeric substance that the equivalent unit of 9-dioctyl fluorine and BTD (F8-BTD) forms, wherein BTD (F8-BTD) is purchased from the fast company of Sang Mumai (Sumation).
Fig. 4 A to 4C is illustrated in the example 6(P4 in chlorobenzene solution after 468nm laser excitation, F22-BSeD-30) polymkeric substance, example 4(F22-BTD-30) polymkeric substance and example 7(P5, F22-NTD-10) the temporal resolution decay of luminescence spectrum of polymkeric substance.In each case, the detection wavelength is made as and approaches Emission Spectrum Peals, and makes the single index decay of the following form of data fitting:
A(t)＝C?exp(-(t/τ))
Observation is used this functional form usually to indicate the leading single order relaxation that is derived from single excited state to exist to the matching that is satisfied with of data.The single index matching is extremely useful, because it distributes to the decay of luminescence process by the leading time constant.
From the temporal resolution decay of the film of polymer materials shown in Fig. 5 A to 5C.In some cases, be fitted to the matching be entirely satisfactory that the single index function does not cause the decay of luminescence curve.This normally indicates a plurality of competition energy or charge transfer process in film or a plurality of emissions position.Alleviating these effects may be complicated a little.In order to compare in the future, we use two exponential forms on the phenomenon level for data modeling:
A(t)＝C 1exp(-(t/τ 1))+C 2exp(-(t/τ 2)
A kind of situation (example 7, F22-NTD-10) under, the extension exponential fitting has following form:
A(t)＝C?exp(-(t/τ) a)
This particular form is generally used for describing the sample that presents a large amount of rate constants, and the film data are used this function to present the interchain interaction that causes the interchain energy migration through this true hint existence of improved matching.Time constant through matching presents in table 4.
Figure BDA0000402055780000231
Example 13: the charge transfer that energy time is differentiated decay and arrived other materials
Purchased from the PVK of aldrich company (Aldrich) via the concentrated solution of the polymkeric substance in methylene dichloride (107mg/ml) in the boiling deionized water repeatedly precipitation obtain purifying.The gained sedimentable matter is dry a couple of days in vacuum drying oven (50 ℃) subsequently, until no longer observe and obtain further weight loss.FIrpic(iridium (III) two (2-(4,6-difluorophenyl) pyridine-N, C2 ') pyridine carboxylic acid is ADS065BE) in statu quo to use.Chlorobenzene is purchased from aldrich company and be in statu quo to use.F8-BT is purchased from the fast company of Sang Mumai and be in statu quo to use.Each prepares PVK, F8-BT and FIrpic (l%w/v) solution naturally in laboratory environment in chlorobenzene.FIrpic:PVK solution mixes corresponding 1% stock solution by the ratio with 0.2:1 and prepares.Subsequently, add 1%F8-BT solution to FIrpic:PVK solution, thereby form F8-BT:FIrpic:PVK solution, its ultimate density ratio is 0.1:0.2:1.Prepared in a similar manner by the solution of other luminescence polymer materials that mix with FIrpic and PVK for spin coating.
The time-resolved emission spectrum of F8-BT (50) and F22-BT (30) is shown in Figure 6, and result is summarized in table 5.To decay in early days (0.5ns to 5ns) be fitted on single index and cause producing for the time constant of the 1.54ns of F8BTD (50) and for the time constant of the 1.87ns of F22-BTD (30).These time constants are very similar with the time constant that obtains the self-cleaning film, and therefore people can not observe any significance degree charge transfer cancellation obtained from the polymkeric substance to the substrate material.
Figure BDA0000402055780000241
All time constants be take ns as unit.
Example 14: use the OLED equipment of constructing with the polymkeric substance of long carbon side chain
Be used for ITO(80nm to the 120nm thickness of the base material of equipment by the patterning on thin (about 0.7mm is thick) sheet glass of l " xl ") form.Therefore cleaning after photoetching process causes producing clean surface usually, and base material is only required in before OLED manufactures and carries out appropriateness and clean.Where necessary, in order to ensure all remaining organic materials removed as photoresistance, all base materials in acetone, the sound wave in 5 minutes in acetone being bathed are carried out other rinsing.Once remove photoresistance, process boat with Teflon so and come the fixing base material the ITO base material is immersed in fully in Virahol (research grade), and ito substrate is placed in ultrasonic bath to 10 minutes.The sound wave carried out in Virahol 10 minutes removes each base material from isopropanol bath, and dries up separately by nitrogen after bathing.Check that base material is in order to guarantee that the ITO base material is not dyeed by solvent residues, and guarantee can not see particle from the teeth outwards.Within 10 minutes, the UV/ ozonize is for final surface cleaning/treatment step.
After the base material preparation, deposition hole injection layer (HIL) on the base material through clean.Through the ITO of UV-ozonize, tend to along with time-evolution (evolve over time), therefore, this step should complete clean after execution immediately.This layer has two major functions, that is, it makes the ITO layer smoothly and the hole injection in impelling from ITO to the active coating.At present, have that to be selected from the various HIL that buy by many suppliers available.In the equipment of constructing at this paper, use prepared PEDOT:PSS (HC Stark CH8000) solution.After hole injection layer deposition, in air with 130 ℃ of (coated) base materials that toast through coating.
After deposition HIL, the poly-fluorenes that deposition contains 50%F8 fluorenes and 50%TFB unit-triarylamine multipolymer F8-TFB, this multipolymer is purchased from the fast company of Sang Mumai.This polymkeric substance dissolves in toluene and dimethylbenzene, and 0.5% (5mg/mL) TFB in use toluene is as coating solution.Make TFB be dissolved in toluene under this concentration and need few degree heating or heated solution not.Deposit this solution via spin coating in nitrogen atmosphere after, in nitrogen atmosphere, with 170 ℃, carry out fired sample partly 1/2 hour.
Subsequently, deposit the solution of emitted polymer via spin coating on the base material through the F8-TFB coating.The concentration of these solution in toluene is generally 1.1%w/v(11mg/ml).Carry out deposition material via spin coating by the speed of revolving of about 1000rpm in nitrogen atmosphere.After depositing this layer, sample toasts half (1/2) hour with 130 ℃ under nitrogen.After the baking program, sample is loaded in the bell jar vaporizer.By vaporizer be pumped to 3x10 -6the pressure of holder, and the Potassium monofluoride layer (nominal thickness<5nm) of deposition of thin subsequently, then (>100nm of deposition of thick) aluminium lamination.Described equipment is sealed by the UV curing adhesive subsequently, and from nitrogen atmosphere, removes in order to tested.
Equipment is that F22-BTD10, F22-BseD10, F22-NTD10 construct as emission layer with three kinds of different polymer materialss.Present electroluminescent with the equipment of every kind in emissive material emissive material structure applying voltage after, wherein measured external quantum efficiency, be that EQE(is defined as launched photon and the ratio of the number of electrons of injecting) be approximately 0.2% and approximately variation between 1.5%.Use is carried out spectral measurement through the Spectra Scan PR705 spectrograph (photo research company (Photo Research)) of calibration in 400nm to 750nm scope.Table 6 is used the spectroscopic data in 400nm to 750nm scope to report the maximum EQE of measured OLED equipment and the average emitted wavelength of calculating.
Figure BDA0000402055780000261
The electroluminescent spectrum of measuring for the equipment that uses three kinds of differing materials to construct is shown in Figure 7.
Although this paper only illustrates and explain some feature of the present invention, those skilled in the art will expect many modifications and change.Therefore, will be appreciated that, appended claims is that intention covers all modifications and the change in true spirit scope of the present invention.

Claims (31)

1. an optoelectronic device, described optoelectronic device has the electroluminescence layer that comprises the polymkeric substance that contains formula I and II structural unit,
Figure FDA0000402055770000011
Wherein, R 1and R 2be C independently 22-44alkyl, the C that contains one or more S, N, O, P or Si atom 22-44alkyl, oxa alkyl heteroaryl or its combination;
R 3and R 4be H independently, C 1-44alkyl or the C that contains one or more S, N, O, P or Si atom 1-44alkyl, or R 3and R 4combine to form and contain the nearly C of three S, N, O, P or Si hetero atoms 2-10monocycle or dicyclo; And
X is S, Se or its combination.
2. optoelectronic device according to claim 1, wherein X is S.
3. optoelectronic device according to claim 1, wherein X is Se.
4. optoelectronic device according to claim 1, wherein R 1and R 2c 22-44alkyl.
5. optoelectronic device according to claim 1, wherein R 1and R 2be-Ar (OCH 2cH 2(CH 2) m) noR 5,
Wherein, m is 0 or 1;
The scope of n is approximately 20 and approximately between 500; And
R 5it is low alkyl group.
6. optoelectronic device according to claim 1, wherein said formula I structural unit is
7. optoelectronic device according to claim 1, wherein said formula I structural unit is
Figure FDA0000402055770000021
R wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5;
M is 0 or 1;
The scope of n is approximately 20 and approximately between 500; And
R 5it is low alkyl group.
8. optoelectronic device according to claim 1, wherein said formula I structural unit is
Figure FDA0000402055770000022
Wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5;
The scope of n is approximately 20 and approximately between 500; And
R 5it is low alkyl group.
9. optoelectronic device according to claim 1, wherein said formula I structural unit is
Figure FDA0000402055770000023
Wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5;
The scope of n is approximately 20 and approximately between 100; And
R 5it is low alkyl group.
10. optoelectronic device according to claim 1, wherein said formula II structural unit is
Figure FDA0000402055770000024
11. optoelectronic device according to claim 1, wherein said formula II structural unit is
12. optoelectronic device according to claim 1, wherein said formula II structural unit is
Figure FDA0000402055770000032
13. a polymkeric substance that comprises formula I and II structural unit,
Figure FDA0000402055770000033
Wherein, R 1and R 2be C independently 22-44alkyl, the C that contains one or more S, N, O, P or Si atom 22-44alkyl, oxa alkyl heteroaryl, or its combination;
R 3and R 4be H independently, C 1-44alkyl or the C that contains one or more S, N, O, P or Si atom 1-44alkyl, or R 3and R 4combine to form and contain the nearly C of three S, N, O, P or Si hetero atoms 2-10monocycle or dicyclo; And
X is S, Se or its combination.
14. polymkeric substance according to claim 13, wherein X is S.
15. polymkeric substance according to claim 13, wherein X is Se.
16. polymkeric substance according to claim 13, wherein R 1and R 2c 22-44.
17. polymkeric substance according to claim 13, wherein R1 and R2 are-Ar (OCH 2cH 2(CH 2) m) noR 5,
Wherein, m is 0 or 1;
The scope of n is approximately 20 and approximately between 500.
18. polymkeric substance according to claim 13, wherein said formula I structural unit is
Figure FDA0000402055770000041
19. polymkeric substance according to claim 13, wherein said formula I structural unit is
Figure FDA0000402055770000042
R wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5;
M is 0 or 1;
The scope of n is approximately 20 and approximately between 500; And
R 5it is low alkyl group.
20. polymkeric substance according to claim 13, wherein said formula I structural unit is
Figure FDA0000402055770000043
Wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5;
The scope of n is approximately 20 and approximately between 500; And
R 5it is low alkyl group.
21. polymkeric substance according to claim 13, wherein said formula I structural unit is
Figure FDA0000402055770000044
Wherein, PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5;
The scope of n is approximately 20 and approximately between 100; And
R5 is low alkyl group.
22. polymkeric substance according to claim 13, wherein said formula II structural unit is
Figure FDA0000402055770000051
23. polymkeric substance according to claim 13, wherein said formula II structural unit is
Figure FDA0000402055770000052
24. polymkeric substance according to claim 13, wherein said formula II structural unit is
Figure FDA0000402055770000053
25. the compound with following formula,
Figure FDA0000402055770000054
R wherein 1aand R 2ashi – (OCH independently 2cH 2(CH 2) m) noR 5;
M is 0 or 1;
The scope of n is approximately 20 and approximately between 500; And
X when occurring, be independently at every turn halogen, trifluoromethayl sulfonic acid ,-B (OH) 2,-B (OR) 2,-BO 2r or its combination; And
R is alkyl or alkylidene group.
26. compound according to claim 25, wherein,
PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5;
The scope of n is approximately 20 and approximately between 500; And
R 5it is low alkyl group.
27. compound according to claim 25, wherein,
PEG Shi – CH 2cH 2(OCH 2cH 2) noR 5;
The scope of n is approximately 20 and approximately between 100; And
R 5it is low alkyl group.
28. optoelectronic device according to claim 1, wherein comprise in addition containing the iridium organometallic compound.
29. optoelectronic device according to claim 28 is wherein said containing iridium organometallic compound and described mixed with polymers.
30. one kind for pure 9, the method for 9-substituted fluorene compound, and described method is included in to exist in the strong acid situation described fluorene compound is contacted with strong oxidizer.
31. method according to claim 30, wherein said strong oxidizer is chromic oxide.
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